Molecular sieve compositions

ABSTRACT

Crystalline molecular sieves having three-dimensional microporous framework structures of MO 2   n , AlO 2 , and PO 2  tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: 
     
         mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 
    
     wherein &#34;R&#34; represents at least one organic templating agent present in the intracrystalline pore system; &#34;M&#34; represents iron and/or titanium, and at least one of cobalt, magnesium, manganese and zinc; &#34;n&#34; is 0, -1 or -2; &#34;m&#34; represents the molar amount of &#34;R&#34; present per mole of (M x  Al y  P z )O 2  ; and &#34;x&#34;, &#34;y&#34; and &#34;z&#34; represent the mole fractions of &#34;M&#34;, aluminum and phosphorus, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 902,020,filed Sept. 2, 1986, now abandoned, which in turn is a continuation ofapplication Ser. No. 599,810, now abandoned, filed Apr. 13, 1984.

FIELD OF THE INVENTION

The instant invention relates to a novel class of crystallinemicroporous molecular sieves, to the method of their preparation. Theinvention relates to novel molecular sieves which contain frameworktetrahedral oxide units of: aluminum; phosphorus; iron and/or titanium;and at least one of cobalt, magnesium, manganese and zinc. Thesecompositions may be prepared hydrothermally from gels containingreactive compounds of the aforementioned elements capable of formingframework tetrahedral oxides, and preferably at least one organictemplating agent which functions in part to determine the course of thecrystallization mechanism and the structure of the crystalline product.

BACKGROUND OF THE INVENTION

Molecular sieves of the crystalline aluminosilicate zeolite type arewell known in the art and now comprise over 150 species of bothnaturally occurring and synthetic compositions. In general thecrystalline zeolites are formed from corner-sharing AlO₂ and SiO₂tetrahedra and are characterized by having pore openings of uniformdimensions, having a significant ion-exchange capacity and being capableof reversibly desorbing an adsorbed phase which is dispersed throughoutthe internal voids of the crystal without displacing any atoms whichmake up the permanent crystal structure.

Other crystalline microporous compositions which are not zeolitic, i.e.do not contain AlO₂ tetrahedra as essential framework constituents, butwhich exhibit the ion-exchange and/or adsorption characteristics of thezeolites are also known. Metal organosilicates which are said to possession-exchange properties, have uniform pores and are capable ofreversibly adsorbing molecules having molecular diameters of about 6 Åor less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 toDwyer et al. A pure silica polymorph, silicalite, having molecularsieving properties and a neutral framework containing neither cationsnor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6,1977 to R. W. Grose et al.

A recently reported class of microporous compositions and the firstframework oxide molecular sieves synthesized without silica, are thecrystalline aluminophosphate compositions disclosed in U.S. Pat. No.4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials areformed from AlO₂ and PO₂ tetrahedra and have electrovalently neutralframeworks as in the case of silica polymorphs. Unlike the silicamolecular sieve, silicalite, which is hydrophobic due to the absence ofextra-structural cations, the aluminophosphate molecular sieves aremoderately hydrophilic, apparently due to the difference inelectronegativity between aluminum and phosphorus. Theirintracrystalline pore volumes and pore diameters are comparable to thoseknown for zeolites and silica molecular sieves.

In copending and commonly assigned application Ser. No. 400,438, filedJuly 26, 1982 (now U.S. Pat. No. 4,440,871), there is described a novelclass of silicon-substituted aluminophosphates which are bothmicroporous and crystalline. The materials have a three dimensionalcrystal framework of PO₂ ⁺, AlO₂ ⁻ and SiO₂ tetrahedral units and,exclusive of any alkali metal or calcium which may optionally bepresent, an as-synthesized empirical chemical composition on ananhydrous basis of:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular silicoaluminophosphate species involved;and "x", "y", and "z" represent the mole fractions of silicon, aluminumand phosphorus, respectively, present as tetrahedral oxides. The minimumvalue for each of "x", "y", and "z" is 0.01 and preferably 0.02. Themaximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52.These silicoaluminophosphates exhibit several physical and chemicalproperties which are characteristic of aluminosilicate zeolites andaluminophosphates.

In copending and commonly assigned application Ser. No. 480,738, filedMar. 31, 1983 (now U.S. Pat. No. 4,500,651) there is described a novelclass of titanium-containing molecular sieves (denominated therein as"TAPO" or "TAPOs") whose chemical composition in the as-synthesized andanhydrous form is represented by the unit empirical formula:

    mR:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Ti_(x) Al_(y) P_(z))O₂ and has a value of betweenzero and about 5.0; and "x", "y" and "z" represent the mole fractions oftitanium, aluminum and phosphorus, respectively, present as tetrahedraloxides.

In copending and commonly assigned application Ser. No. 514,334, filedJuly 15, 1983 (now U.S. Pat. No. 4,567,029) there is described a novelclass of crystalline metal aluminophosphates (denominated therein as"MeAPO" or "MeAPOs") having three-dimensional microporous frameworkstructures of MO₂, AlO₂ and PO₂ tetrahedral units and having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; "M" represents at least one metal of the group magnesium,manganese, zinc and cobalt; "x", "y" and "z" represent the mole fractionof the metal "M", aluminum and phosphorus, respectively, present astetrahedral oxides.

In copending and commonly assigned application Ser. No. 514,335, filedJuly 15, 1983 (now U.S. Pat. No. 4,683,217). there is described a novelclass of crystalline ferroaluminophosphates (denominated therein as"FAPO" or "FAPOs") having a three-dimensional microporous frameworkstructure of FeO₂, AlO₂ and PO₂ tetrahedral units and having anempirical chemical composition on a anhydrous basis expressed by theformula

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3; and "x", "y" and "z" represent the mole fraction of the iron,aluminum and phosphorous, respectively, present as tetrahedral oxides.

The instant invention relates to new molecular sieve compositions whichcomprise framework tetrahedral units of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ ;where "M" represents iron and/or titanium, and at least one of cobalt,magnesium, manganese and zinc, and where "n" is 0, -1 or -2.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ternary diagram wherein parameters relating to the instantcompositions are set forth as mole fractions.

FIG. 2 is a ternary diagram wherein parameters relating to preferredcompositions are set forth as mole fractions.

FIG. 3 is a ternary diagram wherein parameters relating to the reactionmixtures employed in the preparation of the compositions of thisinvention are set forth as mole fractions.

SUMMARY OF THE INVENTION

The instant invention relates to a new class of molecular sieves havinga crystal framework structure of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedraloxide units wherein "M" represents iron and/or titanium, and at leastone of cobalt, magnesium, manganese and zinc, and where "n" is 0, -1 or-2. These new molecular sieves exhibit ion-exchange, adsorption andcatalytic properties and, accordingly, find wide use as adsorbents andcatalysts. The members of this novel class of compositions have crystalframework structures of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral units andhave an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents at least one elementfrom each of the two classes of: (1) iron and titanium; and (2) cobalt,magnesium, manganese and zinc; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; and "x", "y" and "z" represent the mole fractions of "M",aluminum and phosphorus, respectively, present as tetrahedral oxides.These molecular sieve compositions comprise crystalline molecular sieveshaving a three-dimensional microporous framework structure of MO₂ ^(n),AlO₂ ⁻ and PO₂ ⁺ tetrahedral units, wherein "MO₂ ^(n) " representstetrahedral units of iron and/or titanium, and at least one of cobalt,magnesium, manganese and zinc.

The molecular sieves of the instant invention will be generally referredto by the acronym "XAPO" to designate molecular sieves having athree-dimensional microporous framework of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺tetrahedral oxide units as described herein. Actual class members willbe identified by denominating the various structural species which makeup the XAPO class by assigning a number and by replacing "X" by theelements present as tetrahedral oxides with aluminum and phosphorus and,accordingly, e.g., are identified as "XAPO-i" wherein "i" is an integer.This designation is an arbitrary one and is not intended to denotestructural relationship to another material(s) which may also becharacterized by a numbering system.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a new class of molecular sievescomprising crystal framework structures of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺tetrahedral units where "n" is 0, -1 or -2 and where "M" represents atleast one element from each of the two classes of: (1) iron andtitanium; and (2) cobalt, magnesium, manganese and zinc. These newmolecular sieves exhibit ion-exchange, adsorption and catalyticproperties and, accordingly, find wide use as adsorbents and catalysts.

The members of this novel class of compositions have a crystal frameworkstructure of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral oxide units and havean empirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents at least two elementsfrom the two classes of: (1) iron and titanium; and (2) cobalt,magnesium, manganese and zinc; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; "x", "y" and "z" represent the mole fractions of "M",aluminum and phosphorus, respectively, present as tetrahedral oxides.The mole fractions "x", "y", and "z" are generally defined as beingwithin the pentagonal compositional area defined by points A, B, C, D,and E of the ternary diagram of FIG. 1. Points A, B, C, D, and E of FIG.1 have the following values for "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.02          0.60   0.38                                            B        0.02          0.38   0.60                                            C        0.39          0.01   0.60                                            D        0.98          0.01   0.01                                            E        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the molecular sieves the values of "x", "y"and "z" in the above formula are within the hexagonal compositional areadefined by the points a, b, c, d, e, and f of the ternary diagram whichis FIG. 2 of the drawings, said points a, b, c, d, e, and f representingthe following values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.02          0.60   0.38                                            b        0.02          0.38   0.60                                            c        0.39          0.01   0.60                                            d        0.60          0.01   0.39                                            e        0.60          0.39   0.01                                            f        0.39          0.60   0.01                                            ______________________________________                                    

The XAPO molecular sieves of this invention are useful as adsorbents,catalysts, ion-exchangers, and the like in much the same fashion asaluminosilicates have been employed heretofore, although their chemicaland physical properties are not necessarily similar to those observedfor aluminosilicates.

XAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources of"M", aluminum and phosphorus, preferably an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and/or optionally an alkali metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C. until crystals of the XAPO product are obtained, usuallya period of from hours to several weeks. Typical crystallization timesare from about 2 hours to about 30 days with from about 2 hours to about20 days typically being employed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the compositions of the instant invention, it ispreferred to employ a reaction mixture composition expressed in terms ofthe molar ratios as follows:

    aR:(M.sub.u Al.sub.v P.sub.w)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "M" represents at least one element from each of the twoclasses of: (1) iron and titanium; and (2) cobalt, magnesium, manganeseand zinc; "b" has a value of from zero (0) to about 500, preferablybetween 2 and about 300; and "u", "v" and "w" represent the molefractions of "M" (iron and/or titanium, and at least one of cobalt,magnesium, manganese and zinc), aluminum and phosphorus, respectively,in the (M_(u) Al_(v) P_(w))O₂ constituent, and each has a value of atleast 0.01 with the proviso that "x" has a value of at least 0.02; and"x", "y" and "z" are preferably within the pentagonal compositional areadefined by points F, G, H, I and J which is shown in FIG. 3 of thedrawings, the points F, G, H, I and J representing the following valuesfor "u", "v" and "w":

    ______________________________________                                               Mole Fraction                                                          Point    u             v      w                                               ______________________________________                                        F        0.02          0.60   0.38                                            G        0.02          0.38   0.60                                            H        0.39          0.01   0.60                                            I        0.98          0.01   0.01                                            J        0.39          0.60   0.01                                            ______________________________________                                    

In the aforementioned expression of the reaction composition, thereactants are normalized with respect to a total of (x+y+z)=1.00 mole,whereas in some examples the reaction mixtures may be expressed in termsof molar oxide ratios and may be normalized to 1.00 mole of P₂ O₅. Thislatter form is readily converted to the former by routine calculationsby dividing the total number of moles of "M", aluminum and phosphorusinto the moles of each of "M", aluminum and phosphorus. The moles oftemplate and water may be similarly normalized by dividing by the totalmoles of "M", aluminum and phosphorus.

In forming the reaction mixture from which the instant molecular sievesare formed the organic templating agent can be any of those heretoforeproposed for use in the synthesis of conventional zeolitealuminosilicates. In general these compounds contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen, phosphorus,arsenic and antimony, preferably nitrogen or phosphorus and mostpreferably nitrogen, which compounds also contain at least one alkyl oraryl group having from 1 to 8 carbon atoms. Particularly preferredcompounds for use as templating agents are the amines, quaternaryphosphonium compounds and quaternary ammonium compounds, the latter twobeing represented generally by the formula R₄ X⁺ wherein "X" isphosphorous or nitrogen and each R is an alkyl or aryl group containingfrom 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as[(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein "x" has a value of at least 2 are alsosuitably employed. The mono-, di- and tri-amines are advantageouslyutilized, either alone or in combination with a quaternary ammoniumcompound or other templating compound. Mixtures of two or moretemplating agents can either produce mixtures of the desired product orthe more strongly directing templating species may control the course ofthe reaction with the other templating species serving primarily toestablish the pH conditions of the reaction gel. Representativetemplating agents include tetramethylammonium, tetraethylammonium,tetrapropylammonium or tetrabutylammonium ions; tetrapentylammonium ion;di-n-propylamine; tripropylamine; triethylamine; triethanolamine;piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine;1,4-diazabicyclo(2,2,2,) octane; N-methyldiethanolamine,N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl-1,4-diazabicyclo(2,2,2) octane ion;di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Notevery templating agent will direct the formation of every species ofXAPO, i.e., a single templating agent can, with proper manipulation ofthe reaction conditions, direct the formation of several XAPOcompositions, and a given XAPO composition can be produced using severaldifferent templating agents.

The reactive phosphorus source is preferably phosphoric acid, butorganic phosphates such as triethyl phosphate have been foundsatisfactory, and so also have crystalline or amorphousaluminophosphates such as the AlPO₄ compositions of U.S. Pat. No.4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphoniumbromide do not, apparently, serve as reactive sources of phosphorus, butthese compounds do function as templating agents. Conventionalphosphorus salts such as sodium metaphosphate, may be used, at least inpart, as the phosphorus source, but are not preferred.

The preferred aluminum source is either an aluminum alkoxide, such asaluminum isoproproxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorus are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The reactive source of iron can be introduced into the reaction systemin any form which permits the formation in situ of reactive ferrous orferric ions capable of forming the framework tetrahedral unit of FeO₂.Advantageously, iron compounds including oxides, hydroxides, sulfates,acetates, nitrates and the like may be employed. Other reactive sourcesof iron include freshly precipiated iron oxide and gamma-FeOOH may beemployed.

The reactive source of titanium can be introduced into the reactionsystem in any form which permits the formation in situ of reactivetitanium capable of forming the TiO₂ framework tetrahedral unit.Titanium compounds which may be employed herein include titaniumalkoxides, titanium halides, e.g., titanium tetrachloride, water-solubletitanates, titanium chelates and the like.

The reactive source of coalt, magnesium, manganese and zinc can beintroduced into the reaction system in any form which permits theformation in situ of reactive ions of cobalt, magnesium, manganese andzinc capable of forming the framework tetrahedral units of such.Advantageously, salts, oxides, alkoxides or hydroxides of metals areemployed such as cobalt chloride hexahydrate, alpha cobaltous iodide,cobaltous sulfate, cobalt acetate, cobaltous bromide, cobaltouschloride, zinc acetate, zinc bromide, zinc formate, zinc iodide, zincsulfate heptahydrate, magnesium acetate, magnesium bromide, magnesiumchloride, magnesium iodide, magnesium nitrate, magnesium sulfate,manganous acetate, manganous bromide, manganous sulfate and the like.

While not essential to the synthesis of XAPO compositions, stirring orother moderate agitation of the reaction mixture and/or seeding thereaction mixture with seed crystals of either the XAPO species to beproduced or a topologically similar aluminophosphate, aluminosilicate ormolecular sieve composition, facilitates the crystallization procedure.

After crystallization the XAPO product may be isolated andadvantageously washed with water and dried in air. The as-synthesizedXAPO generally contains within its internal pore system at least oneform of the templating agent employed in its formation. Most commonlythe organic moiety is present, at least in part, as a charge-balancingcation as is generally the case with as-synthesized aluminosilicatezeolites prepared from organic-containing reaction systems. It ispossible, however, that some or all of the organic moiety is an occludedmolecular species in a particular XAPO species. As a general rule thetemplating agent, and hence any occluded organic species, is too largeto move freely through the pore system of the XAPO product and must beremoved by calcining the XAPO at temperatures of 200° C. to 700° C. tothermally degrade the organic species. In a few instances the pores ofthe XAPO product are sufficiently large to permit transport of thetemplating agent, particularly if the latter is a small molecule, andaccordingly complete or partial removal thereof can be accomplished byconventional desorption procedures such as carried out in the case ofzeolites. It will be understood that the term "as-synthesized" as usedherein does not include the condition of the XAPO phase wherein theorganic moiety occupying the intracrystalline pore system as a result ofthe hydrothermal crystallization process has been reduced bypost-synthesis treatment such that the value of "m" in the compositionformula

    mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an alkoxide isemployed as the source of "M", aluminum or phosphorus, the correspondingalcohol is necessarily present in the reaction mixture since it is ahydrolysis product of the alkoxide. It has not been determined whetherthis alcohol participates in the synthesis process as a templatingagent. For the purposes of this application, however, this alcohol isarbitrarily omitted from the class of templating agents, even if it ispresent in the as-synthesized XAPO material.

Since the present XAPO compositions are formed from MO₂ ^(n), AlO₂ andPO₂ tetrahedral units which, respectively, have a net charge of "n" (0,-1 or -2), -1 and +1, the matter of cation exchangeability isconsiderably more complicated than in the case of zeolitic molecularsieves in which, ideally, there is a stoichiometric relationship betweenAlO₂ ⁻ tetrahedra and charge-balancing cations. In the instantcompositions, an AlO₂ ⁻ tetrahedron can be balanced electrically eitherby association with a PO₂ ⁺ tetrahedron or a simple cation such as analkali metal cation, a proton (H⁺), a cation of "M" present in thereaction mixture, or an organic cation derived from the templatingagent. Similarly a MO₂ ^(n) tetrahedron can be balanced electrically byassociation with PO₂ ⁺ tetrahedra, a cation of "M" present in thereaction mixture, a simple cation such as an alkali metal cation, aproton (H⁺), organic cations derived from the templating agent, or otherdivalent or polyvalent metal cations introduced from an extraneoussource. It has also been postulated that non-adjacent AlO₂ ⁻ and PO₂ ⁺tetrahedral pairs can be balanced by Na⁺ and OH⁻, respectively [Flanigenand Grose, Molecular Sieve Zeolites-I, ACS, Washington, DC (1971)].

The XAPO compositions of the present invention may exhibitcation-exchange capacity when analyzed using ion-exchange techniquesheretofore employed with zeolitic aluminosilicates and have porediameters which are inherent in the lattice structure of each speciesand which are at least about 3 Å in diameter. Ion exchange of XAPOcompositions is ordinarily possible only after any organic moietyderived from the template, present as a result of synthesis has beenremoved from the pore system. Dehydration to remove water present in theas-synthesized XAPO compositions can usually be accomplished, to somedegree at least, in the usual manner without removal of the organicmoiety, but the absence of the organic species greatly facilitatesadsorption and desorption procedures. The XAPO materials have variousdegrees of hydrothermal and thermal stability, some being quiteremarkable in this regard, and function well as molecular sieveadsorbents and hydrocarbon conversion catalysts or catalyst bases.

In preparing the XAPO composition it is preferred to use a stainlesssteel reaction vessel lined with an inert plastic material, e.g.,polytetrafluoroethylene, to avoid contamination of the reaction mixture.In general, the final reaction mixture from which each XAPO compositionis crystallized is prepared by forming mixtures of less than all of thereagents and thereafter incorporating into these mixtures additionalreagents either singly or in the form of other intermediate mixtures oftwo or more reagents. In some instances the reagents admixed retaintheir identity in the intermediate mixture and in other cases some orall of the reagents are involved in chemical reactions to produce newreagents. The term "mixture" is applied in both cases. Further, it ispreferred that the intermediate mixtures as well as the final reactionmixtures be stirred until substantially homogeneous.

X-ray patterns of reaction products are obtained by X-ray analysis usingstandard X-ray powder diffraction techniques. The radiation source is ahigh-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma.The diffraction pattern from the copper K-alpha radiation and graphitemonochromator is suitably recorded by an X-ray spectrometerscintillation counter, pulse height analyzer and strip chart recorder.Flat compressed powder samples are scanned at 2° (2 theta) per minute,using a two second time constant. Interplanar spacings (d) in Angstromunits are obtained from the position of the diffraction peaks expressedas 2 θ where θ is the Bragg angle as observed on the strip chart.Intensities are determined from the heights of diffraction peaks aftersubtracting background, "I_(o) " being the intensity of the strongestline or peak, and "I" being the intensity of each of the other peaks.Alternatively, the X-ray patterns may be obtained by use of computerbased techniques using Copper K-alpha radiation with Sieman's Type K-805X-ray sources and with Siemens D-500 X-ray powder diffractometersavailable from Siemens Corporation, Cherry Hill, NJ.

As will be understood by those skilled in the art the determination ofthe parameter 2 theta is subject to both human and mechanical error,which in combination, can impose an uncertainty of about ±0.4° on eachreported value of 2 theta. This uncertainty is, of course, alsomanifested in the reported values of the d-spacings, which arecalculated from the 2 theta values. This imprecision is generalthroughout the art and is not sufficient to preclude the differentiationof the present crystalline materials from each other and from thecompositions of the prior art. In some of the X-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, w and vw which represent very strong, strong,medium, weak and very weak, respectively.

In certain instances the purity of a synthesized product may be assessedwith reference to its X-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that theX-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present.

The molecular sieves of the instant invention may be characterized bytheir x-ray powder diffraction patterns and such may have one of thex-ray patterns set forth in the following Tables A through V, whereinsaid x-ray patterns are for both the as-synthesized and calcined formsunless otherwise noted:

                  TABLE A                                                         ______________________________________                                        (XAPO-5)                                                                      2θ     d(Å)  Relative Intensity                                     ______________________________________                                         7.3-7.65     12.1-11.56                                                                             m-vs                                                    19.5-19.95  4.55-4.46 m-s                                                    20.9-21.3    4.25-4.17 m-vs                                                   22.2-22.6    4.00-3.93 w-vs                                                    25.7-26.15  3.47-3.40 w-m                                                    ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        (XAPO-11)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.3-9.65    9.51-9.17 m-s                                                    20.2-20.6    4.40-4.31 m-s                                                    20.9-21.3    4.25-4.17 s-vs                                                   22.0-22.5    4.04-3.95 m-s                                                    22.5-22.9    3.95-3.92 m-s                                                    23.0-23.4    3.87-3.80 m-vs                                                   ______________________________________                                    

                  TABLE C                                                         ______________________________________                                        (XAPO-14)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.6-8.9      10.3-9.93 vs                                                     13.0         6.81      w                                                      21.9-22.2    4.06-4.00 w                                                      25.4         3.51      w                                                      27.5         3.24      w                                                      29.7         3.01      w                                                      ______________________________________                                    

                  TABLE D                                                         ______________________________________                                        (XAPO-16)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        11.3-11.6    7.83-7.63 m-vs                                                   18.7-18.9    4.75-4.70 w-s                                                    21.9-22.3    4.06-3.99 m-vs                                                   26.5-27.0    3.363-3.302                                                                             w-m                                                     29.7-30.05  3.008-2.974                                                                             w-m                                                    ______________________________________                                    

                  TABLE E                                                         ______________________________________                                        (XAPO-17)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.7-7.75     11.5-11.4 vs                                                     13.4         6.61      s-vs                                                   15.5-15.55   5.72-5.70 s                                                      19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                     31.8-32.00   2.812-2.797                                                                             w-s                                                    ______________________________________                                    

                  TABLE F                                                         ______________________________________                                        (XAPO-18)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.6-9.65    9.21-9.16 vs                                                      15.5-15.55  5.72-5.70 m                                                      16.9-17.1    5.25-5.19 m                                                      20.15-20.25  4.41-4.39 m                                                      20.95-21.05  4.24-4.22 m                                                      31.8-32.5    2.814-2.755                                                                             m                                                      ______________________________________                                    

                  TABLE G                                                         ______________________________________                                        (XAPO-20)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                         13.7-14.25  6.46-6.22 m-vs                                                   19.55-20.0   4.54-4.44 w-s                                                    24.05-24.5   3.70-3.63 m-vs                                                   34.3-35.0    2.614-2.564                                                                             vw-w                                                   42.5-43.0    2.127-2.103                                                                             vw-w                                                   ______________________________________                                    

                  TABLE H                                                         ______________________________________                                        (XAPO-31)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.5-8.6      10.40-10.28                                                                             m-s                                                    20.2-20.3    4.40-4.37 m                                                      21.9-22.1    4.06-4.02 w-m                                                    22.6-22.7    3.93-3.92 vs                                                     31.7-31.8    2.823-2.814                                                                             w-m                                                    ______________________________________                                    

                  TABLE J*                                                        ______________________________________                                        (XAPO-33)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.25-9.55    9.56-9.26 w-m                                                    12.5-12.9    7.08-6.86 vs                                                     16.9-17.3    5.25-5.13 w-m                                                    20.45-20.9   4.34-4.25 w-m                                                    23.85-24.25  3.73-3.67 w-m                                                    26.05-26.35  3.42-3.38 w-m                                                    27.3-27.6    3.27-3.23 vs                                                     ______________________________________                                         *as-synthesized form                                                     

                  TABLE K*                                                        ______________________________________                                        (XAPO-33)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        13.15-13.4   6.73-6.61 vs                                                     18.05-18.35  4.91-4.83 m                                                      18.4-18.6    4.82-4.77 m                                                      26.55-26.7   3.36-3.34 m                                                      32.0-32.1    2.80-2.79 m                                                      ______________________________________                                         *calcined form                                                           

                  TABLE L                                                         ______________________________________                                        (XAPO-34)                                                                     2θ     d(Å) Relative Intensity                                      ______________________________________                                         9.4-9.65    9.41-9.17                                                                              s-vs                                                    15.9-16.2    5.57-5.47                                                                              vw-m                                                    17.85-18.4   4.97-4.82                                                                              w-s                                                     20.3-20.9    4.37-4.25                                                                              m-vs                                                    24.95-25.4   3.57-3.51                                                                              vw-s                                                    30.3-30.8    2.95-2.90                                                                              w-s                                                     ______________________________________                                    

                  TABLE M                                                         ______________________________________                                        (XAPO-35)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        10.8-11.1    8.19-7.97 m                                                      17.2-17.4    5.16-5.10 s-vs                                                    21.0-21.25  4.23-4.18 m-s                                                    21.8-22.0    4.08-4.04 vs                                                     31.8-32.2    2.814-2.788                                                                             m                                                      ______________________________________                                    

                  TABLE N                                                         ______________________________________                                        (XAPO-36)                                                                     2θ     d(Å) Relative Intensity                                      ______________________________________                                        7.7-7.9      11.5-11.2                                                                              vs                                                      16.2-16.6    5.47-5.34                                                                              w-m                                                     18.9-19.3    4.70-4.60                                                                              m-s                                                     20.6-20.8    4.31-4.27                                                                              w-s                                                     21.8-22.0    4.08-4.04                                                                              m                                                       22.2-22.5    4.00-3.95                                                                              w-m                                                     ______________________________________                                    

                  TABLE O                                                         ______________________________________                                        (XAPO-37)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        6.1-6.3      14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE P                                                         ______________________________________                                        (XAPO-39)                                                                     2θ     d(Å) Relative Intensity                                      ______________________________________                                        9.4-9.6      9.41-9.21                                                                              w-m                                                     13.3-13.6    6.66-6.51                                                                              m-vs                                                    18.0-18.4    4.93-4.82                                                                              m                                                       21.2-21.5    4.19-4.13                                                                              m-s                                                     22.5-23.0    3.95-3.87                                                                              s-vs                                                    30.2-30.5    2.96-2.93                                                                              w-m                                                     ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (XAPO-40)                                                                     2θ    d(Å)  Relative Intensity                                      ______________________________________                                        7.5-7.7     11.79-11.48                                                                             vw-m                                                    8.0-8.1     11.05-10.94                                                                             s-vs                                                    12.4-12.5   7.14-7.08 w-vs                                                    13.6-13.8   6.51-6.42 m-s                                                     14.0-14.1   6.33-6.28 w-m                                                     27.8-28.0   3.209-3.187                                                                             w-m                                                     ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (XAPO-41)                                                                     2θ    d(Å)  Relative Intensity                                      ______________________________________                                        13.6-13.8   6.51-6.42 w-m                                                     20.5-20.6   4.33-4.31 w-m                                                     21.1-21.3   4.21-4.17 vs                                                      22.1-22.3   4.02-3.99 m-s                                                     22.8-23.0   3.90-3.86 m                                                       23.1-23.4   3.82-3.80 w-m                                                     25.5-25.9   3.493-3.440                                                                             w-m                                                     ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (XAPO-42)                                                                     2θ      d(Å)  Relative Intensity                                    ______________________________________                                        7.15-7.4      12.36-11.95                                                                             m-vs                                                   12.5-12.7    7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                      30.05-30.25  2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE T                                                         ______________________________________                                        (XAPO-44)                                                                     2θ     d(Å)  Relative Intensity                                     ______________________________________                                        9.4-9.55     9.41-9.26 vs                                                     13.0-13.1    6.81-6.76 w-m                                                    16.0-16.2    5.54-5.47 w-m                                                    20.6-20.85   4.31-4.26 s-vs                                                   24.3-24.4    3.66-3.65 w-vs                                                   30.7-30.95   2.912-2.889                                                                             w-s                                                    ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (XAPO-46)                                                                     2θ    d(Å)  Relative Intensity                                      ______________________________________                                        7.2-8.1     12.3-10.9 vs                                                      21.2-21.8   4.19-4.08 w-m                                                     22.5-23.0   3.95-3.87 vw-m                                                    26.6-27.2   3.351-3.278                                                                             vw-w                                                    28.5-29.0   3.132-3.079                                                                             vw-w                                                    ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        (XAPO-47)                                                                     2.0.        d(Å)  Relative Intensity                                      ______________________________________                                        9.4         9.41      vs                                                      15.9-16.0   5.57-5.54 w-m                                                     20.5-20.6   4.33-4.31 s                                                       24.5-24.7   3.63-3.60 w                                                       25.8-25.9   3.45-3.44 w                                                       30.4-30.5   2.940-2.931                                                                             w                                                       ______________________________________                                    

The following examples are provided to further illustrate the inventionand are not provided to be limiting thereof:

EXAMPLE 1 (Preparation of FeMgAPO-5)

(a) FeMgAPO-5 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 TPA:0.05-0.2 Fe₂ O_(q) :0.1-0.4 MgO:0.5-1.0 Al₂ O₃ :0.5-1.0 P₂O₅ :40-100 H₂ O

where "TPA" denotes tripropylamine and "q" denotes the oxidation stateof iron.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce the FeMgAPO-5 product.Solids are recovered by filtration, washed with water and dried in airat room temperature.

The FeMgAPO-5 product's chemical analysis shows the FeMgAPO-5 productcontains iron, magnesium, aluminum and phosphorus in amounts within thepentagonal compositional area defined by points A, B, C, D, and E ofFIG. 1.

The x-ray powder diffraction pattern of an FeMgAPO-5 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                        7.3-7.65      12.1-11.56                                                                             m-vs                                                   19.5-19.95   4.55-4.46 m-s                                                    20.9-21.3    4.25-4.17 m-vs                                                   22.2-22.6    4.00-3.93 w-vs                                                   25.7-26.15   3.47-3.40 w-m                                                    ______________________________________                                    

(b) The x-ray powder diffraction pattern for a calcined FeMgAPO-5 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined FeMgAPO-5 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                Kinetic    Pressure         Wt. %                                     Adsorbate                                                                             Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                 ______________________________________                                        O.sub.2 3.46       100      -183    7                                         O.sub.2 3.46       750      -183    10                                        Neopentane                                                                            6.2        700      24      4                                         H.sub.2 O                                                                             2.65        4.3     24      4                                         H.sub.2 O                                                                             2.65       20.0     24      12                                        ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of FeMgAPO-5 is greater than 6.2 Å.

EXAMPLE 2 (Preparation of FeMnAPO-11)

(a) FeMnAPO-11 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 DPA:0.05-0.2 Fe₂ O_(q) :0.1-0.4 MnO:0.5-1.0 Al₂ O₃ :0.5-1.0 P₂O₅ :40-100 H₂ O

where "DPA" denotes di-n-propylamine and "q" denotes the oxidationstate(s) of iron.

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce FeMnAPO-11 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The FeMnAPO-11 product's chemical analysis shows the FeMnAPO-11 productcontains iron, manganese, aluminum and phosphorus in amounts within thepentagonal compositional area defined by points A, B, C, D, and E ofFIG. 1.

The x-ray powder diffraction pattern of an FeMnAPO-11 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å) Relative Intensity                                      ______________________________________                                         9.3-9.65    9.51-9.17                                                                              m-s                                                     20.2-20.6    4.40-4.31                                                                              m-s                                                     20.9-21.3    4.25-4.17                                                                              s-vs                                                    22.0-22.5    4.04-3.95                                                                              m-s                                                     22.5-22.9    3.95-3.92                                                                              m-s                                                     23.0-23.4    3.87-3.80                                                                              m-vs                                                    ______________________________________                                    

(b) The x-ray powder diffraction pattern for a calcined FeMnAPO-11 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined FeMnAPO-11 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    5                                        O.sub.2  3.46       750      -183    6                                        Cyclohexane                                                                            6.0         90        24    4                                        H.sub.2 O                                                                              2.65        4.3       24    6                                        H.sub.2 O                                                                              2.65        20        24    8                                        ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of FeMnAPO-11 is about 6 Å.

EXAMPLE 3 (Preparation of FeCoMgAPO-17)

(a) FeCoMgAPO-17 is prepared from a reaction mixture having acomposition, expressed in terms of the molar oxide ratios of thecomponents of the reaction mixture, of:

1.0-2.0 QN:0.05-0.2 M₂ O_(q) :0.5-1.0 Al₂ O₃ :0.5-1.0 P₂ O₅ :40-100 H₂ O

where "QN" denotes quinuclidine and "q" denotes the oxidation states of"M" (iron, cobalt, and magnesium).

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce FeCoMgAPO-17 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The FeCoMgAPO-17 product's chemical analysis shows the FeCoMgAPO-17product contains iron, cobalt, magnesium, aluminum and phosphorus inamounts within the pentagonal compositional area defined by points A, B,C, D, and E of FIG. 1.

The x-ray powder diffraction pattern of a FeCoMgAPO-17 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å) Relative Intensity                                      ______________________________________                                         7.7-7.75    11.5-11.4 vs                                                     13.4         6.61      .sup. s-vs                                              15.5-15.55  5.72-5.70 s                                                      19.65-19.7   4.52-4.51 w-s                                                    20.5-20.6    4.33-4.31 vs                                                      31.8-32.00  2.812-2.797                                                                             w-s                                                    ______________________________________                                    

(b) The x-ray powder diffraction pattern for a calcined FeCoMgAPO-17 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined FeCoMgAPO-17 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    10                                       O.sub.2  3.46       750      -183    12                                       n-butane 4.3        100        24     4                                       H.sub.2 O                                                                              2.65       4.3        24    13                                       H.sub.2 O                                                                              2.65        20        24    14                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of FeCoMgAPO-17 is about 4.3 Å.

EXAMPLE 4 (Preparation of TiZnAPO-31)

(a) TiZnAPO-31 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 DPA:0.05-0.2 M₂ O_(q) :0.5-1.0 Al₂ O₃ :0.5-1.0 P₂ O₅ :40-100 H₂O

wherein "DPA" denotes di-n-propylamine and "q" denotes the oxidationstate(s) of "M" (titanium and zinc).

The reaction mixture is seeded with crystals of AlPO₄ -31 (U.S. Pat. No.4,310,440) and digested by placing the reaction mixture in a sealedstainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce TiZnAPO-31 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The TiZnAPO-31 product's chemical analysis shows the TiZnAPO-31 productcontains titanium, zinc, aluminum and phosphorus in amounts within thepentagonal compositional area defined by points A, B, C, D, and E ofFIG. 1.

The x-ray powder diffraction pattern of a TiZnAPO-31 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                        8.5-8.6      10.40-10.28                                                                             m-s                                                    20.2-20.3    4.40-4.37 m                                                      21.9-22.1    4.06-4.02 w-m                                                    22.6-22.7    3.93-3.92 vs                                                     31.7-31.8    2.823-2.814                                                                             w-m                                                    ______________________________________                                    

(b) The x-ray powder diffraction pattern for a calcined TiZnAPO-31 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined TiZnAPO-31 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    4                                        O.sub.2  3.46       750      -183    6                                        Cyclohexane                                                                            6.0         90      24      3                                        Neopentane                                                                             6.2        700      24      3                                        H.sub.2 O                                                                              2.65       4.3      24      3                                        H.sub.2 O                                                                              2.65        20      24      10                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of TiZnAPO-31 is greater than about 6.2 Å.

EXAMPLE 5 (Preparation of FeTiCoAPO-34)

(a) FeTiCoAPO-34 is prepared from a reaction mixture having acomposition, expressed in terms of the molar oxide ratios of thecomponents of the reaction mixture, of:

1.0-2.0 TEAOH:0.05-0.2 M₂ O_(q) :0.5-1.0 Al₂ O₃ :0.5-1.0 P₂ O₅ :40-100H₂ O

where "TEAOH" denotes tetraethylammonium hydroxide and "q" denotes theoxidation state(s) of "M" (iron, titanium and cobalt).

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce FeTiCoAPO-34 product.The solids are recovered by filtration, washed with water and dried inair at room temperature.

The FeTiCoAPO-34 product's chemical analysis shows the FeTiCoAPO-34product contains iron, titanium, cobalt, aluminum and phosphorus inamounts within the pentagonal compositional area defined by points A, B,C, D, and E of FIG. 1.

The x-ray powder diffraction pattern of an FeTiCoAPO-34 product ischaracterized by the following data:

    ______________________________________                                        2θ      d(Å) Relative Intensity                                     ______________________________________                                         9.4-9.65     9.41-9.17                                                                              s-vs                                                   15.9-16.2     5.57-5.47                                                                              vw-m                                                   17.85-18.4    4.97-4.82                                                                              w-s                                                    20.3-20.9     4.37-4.25                                                                              m-vs                                                   24.95-25.4    3.57-3.51                                                                              vw-s                                                   30.3-30.8     2.95-2.90                                                                              w-s                                                    ______________________________________                                    

(b) The x-ray powder diffraction pattern for a calcined FeTiCoAPO-34 isalso characterized by the X-ray pattern of part (a).

(c) When the calcined FeTiCoAPO-34 of part (b) is utilized in adsorptioncapacity studies using a standard McBain-Bakr gravimetric adsorptionapparatus the measurements are made on a sample after activation at 350°C. in vacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    13                                       O.sub.2  3.46       750      -183    18                                       n-hexane 4.3        100      24       6                                       H.sub.2 O                                                                              2.65       4.3      24      15                                       H.sub.2 O                                                                              2.65        20      24      21                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of FeTiCoAPO-34 is about 4.3 Å.

EXAMPLE 6 (Preparation of FeMnAPO-44)

(a) FeMnAPO-44 is prepared from a reaction mixture having a composition,expressed in terms of the molar oxide ratios of the components of thereaction mixture, of:

1.0-2.0 CHA:0.05-0.2 M₂ O_(q) :0.5-1.0 Al₂ O₃ :0.5-1.0 P₂ O₅ :40-100 H₂O

where "CHA" denotes cyclohexylamine and "q" denotes the oxidation stateof "M" (iron and manganese).

The reaction mixture is digested by placing the reaction mixture in asealed stainless steel pressure vessel and heating it at an effectivetemperature and for an effective time to produce the FeMnAPO-44 product.Solids are then recovered by filtration, washed with water and dried inair at room temperature.

The FeMnAPO-44 product's chemical analysis shows the FeMnAPO-44 productcontains iron, manganese, aluminum and phosphorus in amounts within thepentagonal compositional area defined by points A, B, C, D, and E ofFIG. 1.

The x-ray powder diffraction pattern of an FeMnAPO-44 product ischaracterized by the following data:

    ______________________________________                                        2θ     d(Å)  Relative Intensity                                     ______________________________________                                         9.4-9.55    9.41-9.26 vs                                                     13.0-13.1    6.81-6.76 w-m                                                    16.0-16.2    5.54-5.47 w-m                                                     20.6-20.85  4.31-4.26 s-vs                                                   24.3-24.4    3.66-3.65 w-vs                                                    30.7-30.95  2.912-2.889                                                                             w-s                                                    ______________________________________                                    

(b) When the calcined FeMnAPO-44 is utilized in adsorption capacitystudies using a standard McBain-Bakr gravimetric adsorption apparatusthe measurements are made on a sample after activation at 350° C. invacuum. The following data are used in the adsorption studies:

    ______________________________________                                                 Kinetic    Pressure         Wt. %                                    Adsorbate                                                                              Diameter (Å)                                                                         (Torr)   Temp, °C.                                                                      Adsorbed*                                ______________________________________                                        O.sub.2  3.46       100      -183    13                                       O.sub.2  3.46       750      -183    16                                       n-hexane 4.3        100      24       2                                       H.sub.2 O                                                                              2.65       4.3      24      15                                       H.sub.2 O                                                                              2.65        20      24      17                                       ______________________________________                                         *typical amount adsorbed                                                 

The pore diameter of FeMnAPO-44 is about 4.3 Å.

PROCESS APPLICATIONS

The XAPO compositions of the present invention are, in general,hydrophilic and adsorb water preferentially over common hydrocarbonmolecules such as paraffins, olefins and aromatic species, e.g.,benzene, xylenes and cumene. Thus the present molecular sievecompositions as a class are useful as desiccants in such adsorptionseparation/purification processes as natural gas drying, cracked gasdrying. Water is also preferentially adsorbed over the so-calledpermanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen.These XAPOs are therefore suitably employed in the drying of reformerhydrogen streams and in the drying of oxygen, nitrogen or air prior toliquifaction.

The present XAPO compositions also exhibit novel surface selectivitycharacteristics which render them useful as catalyst or catalyst basesin a number of hydrocarbon conversion and oxidative combustionreactions. They can be impregnated or otherwise loaded withcatalytically active metals by methods well known in the art and used,for example, in fabricating catalyst compositions having silica oralumina bases. Of the general class, those species having pores largerthan about 4 Å are preferred for catalytic applications.

Among the hydrocarbon conversion reactions catalyzed by XAPOcompositions are cracking, hydrocracking, alkylation for both thearomatic and isoparaffin types, isomerization including xyleneisomerization, polymerization, reforming, hydrogenation,dehydrogenation, transalkylation, dealkylation, hydrodecyclization anddehydrocyclization.

Using XAPO catalyst compositions which contain a hydrogenation promotersuch as platinum or palladium, heavy petroleum residual stocks, cyclicstocks and other hydrocrackable charge stocks, can be hydrocracked attemperatures in the range of 400° F. to 825° F. using molar ratios ofhydrogen to hydrocarbon in the range of between 2 and 80, pressuresbetween 10 and 3500 p.s.i.g., and a liquid hourly space velocity (LHSV)of from 0.1 to 20, preferably 1.0 to 10.

The XAPO catalyst compositions employed in hydrocracking are alsosuitable for use in reforming processes in which the hydrocarbonfeedstocks contact the catalyst at temperatures of from about 700° F. to1000° F., hydrogen pressures of from 100 to 500 p.s.i.g., LHSV values inthe range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in therange of 1 to 20, preferably between 4 and 12.

These same catalysts, i.e. those containing hydrogenation promoters, arealso useful in hydroisomerizations processes in which feedstocks such anormal paraffins are converted to saturated branched chain isomers.Hydroisomerization is carried out at a temperature of from about 200° F.to 600° F., preferably 300° F. to 550° F. with an LHSV value of fromabout 0.2 to 1.0. Hydrogen (H) is supplied to the reactor in admixturewith the hydrocarbon (Hc) feedstock in molar proportions (H/Hc) ofbetween 1 and 5.

At somewhat higher temperatures, i.e. from about 650° F. to 1000° F.,preferably 850° F. to 950° F. and usually at somewhat lower pressureswithin the range of about 15 to 50 p.s.i.g., the same catalystcompositions are used to hydroisomerize normal paraffins. Preferably theparaffin feedstock comprises normal paraffins having a carbon numberrange of C₇ -C₂₀. Contact time between the feedstock and the catalyst isgenerally relatively short to avoid undesireable side reactions such asolefin polymerization and paraffin cracking. LHSV values in the range of0.1 to 10, preferably 1.0 to 6.0 are suitable.

The unique crystal structure of the present XAPO catalysts and theiravailability in a form totally void of alkali metal content favor theiruse in the conversion of alkylaromatic compounds, particularly thecatalytic disproportionation of toluene, ethylene, trimethyl benzenes,tetramethyl benzenes and the like. In the disproportionation process,isomerization and transalkylation can also occur. Group VIII noble metaladjuvants alone or in conjunction with Group VI-B metals such astungsten, molybdenum and chromium are preferably included in thecatalyst composition in amounts of from about 3 to 15 weight-% of theoverall composition. Extraneous hydrogen can, but need not, be presentin the reaction zone which is maintained at a temperature of from about400° to 750° F., pressures in the range of 100 to 2000 p.s.i.g. and LHSVvalues in the range of 0.1 to 15.

Catalytic cracking processes are preferably carried out with XAPOcompositions using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc., with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F., LHSV valuesof 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. aresuitable.

Dehydrocyclization reactions employing paraffinic hydrocarbonfeedstocks, preferably normal paraffins having more than 6 carbon atoms,to form benzene, xylenes, toluene and the like are carried out usingessentially the same reaction conditions as for catalytic cracking. Forthese reactions it is preferred to use the XAPO catalyst in conjunctionwith a Group VIII non-noble metal cation such as cobalt and nickel.

In catalytic dealkylation wherein it is desired to cleave paraffinicside chains from aromatic nuclei without substantially hydrogenating thering structure, relatively high temperatures in the range of about800°-1000° F. are employed at moderate hydrogen pressures of about300-1000 p.s.i.g., other conditions being similar to those describedabove for catalytic hydrocracking. Preferred catalysts are of the sametype described above in connection with catalytic dehydrocyclization.Particularly desirable dealkylation reactions contemplated hereininclude the conversion of methylnaphthalene to naphthalene and tolueneand/or xylenes to benzene.

In catalytic hydrofining, the primary objective is to promote theselective hydrodecomposition of organic sulfur and/or nitrogen compoundsin the feed, without substantially affecting hydrocarbon moleculestherein. For this purpose it is preferred to employ the same generalconditions described above for catalytic hydrocracking, and catalysts ofthe same general nature described in connection with dehydrocyclizationoperations. Feedstocks include gasoline fractions, kerosenes, jet fuelfractions, diesel fractions, light and heavy gas oils, deasphalted crudeoil residua and the like any of which may contain up to about 5weight-percent of sulfur and up to about 3 weight-percent of nitrogen.

Similar conditions can be employed to effect hydrofining, i.e.,denitrogenation and desulfurization, of hydrocarbon feeds containingsubstantial proportions of organonitrogen and organosulfur compounds. Itis generally recognized that the presence of substantial amounts of suchconstituents markedly inhibits the activity of hydrocracking catalysts.Consequently, it is necessary to operate at more extreme conditions whenit is desired to obtain the same degree of hydrocracking conversion perpass on a relatively nitrogenous feed than are required with a feedcontaining less organonitrogen compounds. Consequently, the conditionsunder which denitrogenation, desulfurization and/or hydrocracking can bemost expeditiously accomplished in any given situation are necessarilydetermined in view of the characteristics of the feedstocks inparticular the concentration of organonitrogen compounds in thefeedstock. As a result of the effect of organonitrogen compounds on thehydrocracking activity of these compositions it is not at all unlikelythat the conditions most suitable for denitrogenation of a givenfeedstock having a relatively high organonitrogen content with minimalhydrocracking, e.g., less than 20 volume percent of fresh feed per pass,might be the same as those preferred for hydrocracking another feedstockhaving a lower concentration of hydrocracking inhibiting constituentse.g., organonitrogen compounds. Consequently, it has become the practicein this art to establish the conditions under which a certain feed is tobe contacted on the basis of preliminary screening tests with thespecific catalyst and feedstock.

Isomerization reactions are carried out under conditions similar tothose described above for reforming, using somewhat more acidiccatalysts. Olefins are preferably isomerized at temperatures of500°-900° F., while paraffins, naphthenes and alkyl aromatics areisomerized at temperatures of 700°-1000° F. Particularly desirableisomerization reactions contemplated herein include the conversion ofn-heptene and/or n-octane to isoheptanes, iso-octanes, butane toiso-butane, methylcyclopentane to cyclohexane, meta-xylene and/orortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene,n-hexene to isohexene, cyclohexene to methylcyclopentene etc. Thepreferred form of the catalyst is a combination of the XAPO withpolyvalent metal compounds (such as sulfides) of metals of Group II-A,Group II-B and rare earth metals. For alkylation and dealkylationprocesses the XAPO compositions having pores of at least 5 Å arepreferred. When employed for dealkylation of alkyl aromatics, thetemperature is usually at least 350° F. and ranges up to a temperatureat which substantial cracking of the feedstock or conversion productsoccurs, generally up to about 700° F. The temperature is preferably atleast 450° F. and not greater than the critical temperature of thecompound undergoing dealkylation. Pressure conditions are applied toretain at least the aromatic feed in the liquid state. For alkylationthe temperature can be as low as 250° F. but is preferably at least 350°F. In the alkylation of benzene, toluene and xylene, the preferredalkylating agents are olefins such as ethylene and propylene.

We claim:
 1. A crystalline molecular sieve having a three-dimensionalmicroporous framework structure of MO₂ ^(n), AlO₂ and PO₂ tetrahedraloxide units having an empirical chemical composition on an anhydrousbasis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents: (1) titanium, or amixture of titanium and iron; and (2) at least one element from thegroup consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1or -2; "m" represents a molar amount of "R" present per mole of (M_(x)Al_(y) P_(z))O₂ and has a value of zero (0) to about 0.3; and "x", "y"and "z" represent the mole fractions of "M", aluminum and phosphorus,respectively, present as tetrahedral oxides, said mole fractions beingsuch that they are within the pentagonal compositional area defined bypoints A, B, C, D and E of FIG. 1, said crystalline molecular sievehaving a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in one of the following Tables O, Q,R, S and U.

                  TABLE O                                                         ______________________________________                                        (XAPO-37)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         6.1-6.3     14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (XAPO-40)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         7.5-7.7     11.79-11.48                                                                             vw-m                                                   8.0-8.1      11.05-10.94                                                                             s-vs                                                   12.4-12.5    7.14-7.08 w-vs                                                   13.6-13.8    6.51-6.42 m-s                                                    14.0-14.1    6.33-6.28 w-m                                                    27.8-28.0    3.209-3.187                                                                             w-m                                                    ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (XAPO-41)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                        13.6-13.8    6.51-6.42 w-m                                                    20.5-20.6    4.33-4.31 w-m                                                    21.1-21.3    4.21-4.17 vs                                                     22.1-22.3    4.02-3.99 m-s                                                    22.8-23.0    3.90-3.86 m                                                      23.1-23.4    3.82-3.80 w-m                                                    25.5-25.9    3.493-3.440                                                                             w-m                                                    ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (XAPO-42)                                                                     2Θ      D (Å) Relative Intensity                                    ______________________________________                                         7.15-7.4     12.36-11.95                                                                             m-vs                                                  12.5-12.7     7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                     30.05-30.25   2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (XAPO-46)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         7.2-8.1      12.3-10.9                                                                              vs                                                     21.2-21.8    4.19-4.08 w-m                                                    22.5-23.0    3.95-3.87 vw-m                                                   26.6-27.2    3.351-3.278                                                                             vw-w                                                   28.5-29.0    3.132-3.079                                                                             vw-w                                                   ______________________________________                                    


2. Molecular sieves according to claim 1 wherein the mole fractions of"M", aluminum and phosphorus present as tetrahedral oxides are withinthe hexagonal compositional area defined by points a, b, c, d, e and fof FIG.
 2. 3. A process for preparing a molecular sieve having acrystalline three-dimensional microporous framework structure of MO₂^(n), AlO₂ and PO₂ tetrahedral oxide units having an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents: (1) titanium, or amixture of titanium and iron; and (2) at least one element from thegroup consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1or -2; "m" represents a molar amount of "R" present per mole of (M_(x)Al_(y) P_(z))O₂ and has a value of zero (0) to about 0.3; and "x", "y"and "z" represent the mole fractions of "M", aluminum and phosphorus,respectively, present as tetrahedral oxides, said mole fractions beingsuch that they are within the pentagonal compositional area defined bypoints A, B, C, D and E of FIG. 1, said crystalline molecular sievehaving a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in one of the following Tables O, Q,R, S and U.

                  TABLE O                                                         ______________________________________                                        (XAPO-37)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         6.1-6.3      14.49-14.03                                                                            vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (XAPO-40)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         7.5-7.7     11.79-11.48                                                                             vw-m                                                   8.0-8.1      11.05-10.94                                                                             s-vs                                                   12.4-12.5    7.14-7.08 w-vs                                                   13.6-13.8    6.51-6.42 m-s                                                    14.0-14.1    6.33-6.28 w-m                                                    27.8-28.0    3.209-3.187                                                                             w-m                                                    ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (XAPO-41)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                        13.6-13.8    6.51-6.42 w-m                                                    20.5-20.6    4.33-4.31 w-m                                                    21.1-21.3    4.21-4.17 vs                                                     22.1-22.3    4.02-3.99 m-s                                                    22.8-23.0    3.90-3.86 m                                                      23.1-23.4    3.82-3.80 w-m                                                    25.5-25.9    3.493-3.440                                                                             w-m                                                    ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (XAPO-42)                                                                     2Θ      D (Å) Relative Intensity                                    ______________________________________                                         7.15-7.4     12.36-11.95                                                                             m-vs                                                  12.5-12.7     7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                     30.05-30.25   2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (XAPO-46)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         7.2-8.1     12.3-10.9 vs                                                     21.2-21.8    4.19-4.08 w-m                                                    22.5-23.0    3.95-3.87 vw-m                                                   26.6-27.2    3.351-3.278                                                                             vw-w                                                   28.5-29.0    3.132-3.079                                                                             vw-w                                                   ______________________________________                                    

which process comprises providing a reaction mixture composition at aneffective temperature and for an effective time sufficient to producesaid molecular sieve, said reaction mixture composition being expressedin terms of molar oxide ratios as follows:

    aR:(M.sub.u Al.sub.v P.sub.w)O.sub.2 :bH.sub.2 O

where "R" is an organic templating agent; "a" is the amount of "R" andis an effective amount greater than zero to about 6; "M" representstitanium, or a mixture of titanium and iron, and at least one of cobalt,magnesium, manganese and zinc; "b" has a value of between zero and about500; and "u", "v" and "w" represent the mole fractions, respectively, of"M", aluminum and phosphorus in the (M_(u) Al_(v) P_(w))O₂ constituent,and each has a value of at least 0.01.
 4. The process of claim 3 wherein"u", "v" and "w" are within the pentagonal compositional area defined bypoints F, G, H, I and J of FIG.
 3. 5. Process according to claim 3wherein the source of phosphorus in the reaction mixture isorthophosphoric acid.
 6. Process according to claim 3 wherein the sourceof phosphorus in the reaction mixture is orthophosphoric acid and thesource of aluminum is at least one compound selected from the groupconsisting of pseudo-boehmite and aluminum alkoxide.
 7. Processaccording to claim 6 wherein the aluminum alkoxide is aluminumisopropoxide.
 8. Process according to claim 3 wherein the sources oftitanium, iron, cobalt, magnesium, manganese and zinc are selected fromthe group consisting of chlorides, bromides, iodides, oxides,hydroxides, alkoxides, nitrates, sulfates, acetates and mixturesthereof.
 9. Process according to claim 3 wherein the organic templatingagent is a quaternary ammonium or quaternary phosphonium compound havingthe formula:

    R.sub.4 X.sup.+

wherein X is nitrogen or phosphorus and each R is an alkyl or aryl groupcontaining from 1 to 8 carbon atoms.
 10. Process according to claim 3wherein the organic templating agent is an amine.
 11. Process accordingto claim 3 wherein the templating agent is selected from the groupconsisting of tetrapropylammonium ion; tetraethylammonium ion;tripropylamine; triethylamine; triethanolamine; piperidine;cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine;N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine;1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine;N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammoniumion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone;di-n-propylamine; and a polymeric quaternary ammonium salt [(C₁₄ H₃₂ N₂)(OH)₂ ]_(x) wherein x has a value of at least
 2. 12. A molecular sieveprepared by calcining, at a temperature sufficiently high to remove atleast some of the organic templating agent present in theintracrystalline pore system, a crystalline molecular sieve having athree-dimensional microporous framework structure of MO₂ ^(n), AlO₂ andPO₂ tetrahedral oxide units having an empirical chemical composition onan anhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents: (1) titanium, or amixture of titanium and iron; and (2) at least one element from thegroup consisting of cobalt, magnesium, manganese and zinc; "n" is 0, -1or -2; "m" represents a molar amount of "R" present per mole of (M_(x)Al_(y) P_(z))O₂ and has a value of zero (0) to about 0.3; and "x", "y"and "z" represent the mole fractions of "M", aluminum and phosphorus,respectively, present as tetrahedral oxides, said mole fractions beingsuch that they are within the pentagonal compositional area defined bypoints A, B, C, D and E of FIG. 1, said crystalline molecular sievehaving a characteristic X-ray powder diffraction pattern which containsat least the d-spacings set forth in one of the following Tables O, Q,R, S and U.

                  TABLE O                                                         ______________________________________                                        (XAPO-37)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         6.1-6.3     14.49-14.03                                                                             vs                                                     15.5-15.7    5.72-5.64 w-m                                                    18.5-18.8    4.80-4.72 w-m                                                    23.5-23.7    3.79-3.75 w-m                                                    26.9-27.1    3.31-3.29 w-m                                                    ______________________________________                                    

                  TABLE Q                                                         ______________________________________                                        (XAPO-40)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         7.5-7.7     11.79-11.48                                                                             vw-m                                                   8.0-8.1      11.05-10.94                                                                             s-vs                                                   12.4-12.5    7.14-7.08 w-vs                                                   13.6-13.8    6.51-6.42 m-s                                                    14.0-14.1    6.33-6.28 w-m                                                    27.8-28.0    3.209-3.187                                                                             w-m                                                    ______________________________________                                    

                  TABLE R                                                         ______________________________________                                        (XAPO-41)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                        13.6-13.8    6.51-6.42 w-m                                                    20.5-20.6    4.33-4.31 w-m                                                    21.1-21.3    4.21-4.17 vs                                                     22.1-22.3    4.02-3.99 m-s                                                    22.8-23.0    3.90-3.86 m                                                      23.1-23.4    3.82-3.80 w-m                                                    25.5-25.9    3.493-3.440                                                                             w-m                                                    ______________________________________                                    

                  TABLE S                                                         ______________________________________                                        (XAPO-42)                                                                     2Θ      D (Å) Relative Intensity                                    ______________________________________                                         7.15-7.4     12.36-11.95                                                                             m-vs                                                  12.5-12.7     7.08-6.97 m-s                                                   21.75-21.9    4.09-4.06 m-s                                                    24.1-24.25   3.69-3.67 vs                                                    27.25-27.4    3.273-3.255                                                                             s                                                     30.05-30.25   2.974-2.955                                                                             m-s                                                   ______________________________________                                    

                  TABLE U                                                         ______________________________________                                        (XAPO-46)                                                                     2Θ     D (Å) Relative Intensity                                     ______________________________________                                         7.2-8.1     12.3-10.9 vs                                                     21.2-21.8    4.19-4.08 w-m                                                    22.5-23.0    3.95-3.87 vw-m                                                   26.6-27.2    3.351-3.278                                                                             vw-w                                                   28.5-29.0    3.132-3.079                                                                             vw-w                                                   ______________________________________                                    